JPH06711B2 - Benzyl ether derivative and insecticidal and acaricidal agent containing the same as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) [Wherein R ₁ represents a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group, a lower haloalkyl group, a halogen atom or a fluorine-substituted lower alkoxyl group, and R 1
₂ represents a hydrogen atom or a halogen atom, and R ₁ and R
_{And 2} together represent a methylenedioxy group. R ₃ and R ₄ each represent a methyl group, or R ₃ and R ₄ represent an ethylene group or a 1,1-difluoroethylene group.
R ₅ represents a lower alkyl group, a lower haloalkyl group, a lower alkenyl group or a lower alkynyl group, and R ₆ represents a hydrogen atom or a fluorine atom. ] It is related with the benzyl ether derivative shown by these, and the insecticide and acaricide containing it as an active ingredient.

The present inventors have carried out research for the purpose of developing a compound having excellent insecticidal and acaricidal activity, resulting in the general formula (I).
The compound of the present invention represented by Extremely high insecticidal effect. 2. It has no environmental persistence like organochlorine pesticides. 3. Relatively low toxicity to humans and fish. 4. It is also effective against harmful insects that are resistant to organic phosphorus agents or carbamate agents. 5. It can be manufactured relatively inexpensively.

The inventors have found that they have excellent properties such as, and have completed the present invention.

Specific pests for which the compound of the present invention is particularly effective include hemiptera such as planthoppers, leafhoppers, aphids, stink bugs, lepidoptera such as diamondback moth, lizard, and armyworm, diptera such as Culex pipiens and housefly. As a nettle, Coleoptera, Orthoptera, and spider mites of the German cockroach, etc., there can be mentioned the spider mites, citrus spider mites and the like.

The compound of the present invention has the general formula (II) [Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₆ have the same meanings as described above. ] The unsaturated carbinol represented by the general formula (III) [Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₆ have the same meanings as described above. ] To the unsaturated carbinol represented by the formula, and then the carbinol in the presence of a base, the general formula (IV) R ₅ -X (IV) [wherein R ₅ has the same meaning as described above, X is Represents a halogen atom, a tosyloxy group or a mesyloxy group. ] It can be obtained by reacting with a compound represented by

In the above production method, the catalytic reduction reaction is carried out in an inert solvent, and examples of such a solvent include hydrocarbon solvents such as hexane, toluene and benzene, protic polar solvents such as acetic acid, methanol and ethanol, and acetic acid. Examples thereof include ester solvents such as ethyl. Typical examples of the reduction catalyst include palladium-carbon, platinum oxide and the like. The amount of such a reduction catalyst used is 0.3 to 50% W / based on the unsaturated carbinol represented by the general formula (II).
W range, typically 0.5 to 5% W / W range. The reaction temperature is in the range of 0 to 30 ° C, usually around 20 ° C, and the purpose can be sufficiently achieved. The reaction time may vary depending on the amount of catalyst used, but it is usually 1 to 10 hours. The reaction may be performed under pressure or under normal pressure, but the purpose can be sufficiently achieved under normal pressure.

Further, the general formula used in the etherification of the saturated carbinol represented by the general formula (III) thus obtained
The amount of the compound represented by (IV) used is equimolar to 2.0 times the molar amount of the carbinol. As the base, for example, sodium hydride or the like is used, and the amount thereof is 1.0 to 1.2 times the mol of the carbinol. In order to carry out the reaction more smoothly in the reaction, a polar aprotic solvent such as dimethyl sulfoxide or dimethylformamide is usually used. The reaction temperature is optional in the range of 0 to 100 ° C., but usually 15 to 70 ° C. is sufficient for the purpose, and the reaction time is usually 1 to 12 hours.

The unsaturated carbinol represented by the general formula (II) has the general formula (V) [Wherein R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above. ] In the presence of a base, an acetylene compound represented by the general formula (VI) [In the formula, R ₆ has the same meaning as described above. ] It can be obtained by reacting with an aldehyde represented by

The reaction is usually carried out in the presence of an inert solvent, and examples of such a solvent include hydrocarbon solvents such as hexane, benzene and toluene, ether solvents such as tetrahydrofuran and diethyl ether, dimethylformamide,
An aprotic polar solvent such as dimethyl sulfoxide may, for example, be mentioned. The reaction time is arbitrary in the range of −78 ° C. to 100 ° C., but is usually in the range of −40 to 40 ° C. The reaction time is usually 1 to 15 hours, though it varies depending on the reaction temperature. Typical examples of the base used in this reaction include n-butyllithium, sodium hydride, potassium hydride, sodium, ethylmagnesium lithium and the like.

Regarding the molar ratio of these reaction reagents, the acetylene compound is 0.5 to 1.5 times mol, usually 0.8 to 1.2 times mol, relative to the aldehyde, and the base is usually 0.9 to 1.1 times mol relative to the acetylene compound. It is in the molar range.

Furthermore, the acetylene compound represented by the general formula (V) has the general formula (VI) [Wherein R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above. ] From an aldehyde represented by, for example, Tetrahedron LETTER
It can be obtained by the method described in S, 36 , 3769 (1972).

Example 1 of the compound of the present invention produced based on the above method
Although shown in the table, the present invention is not limited to only these examples.

Further, the compound of the present invention has an asymmetric carbon, and each optical isomer exists, but these optically active compounds are also included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Reference Examples.

Synthesis Example 1 4-Methyl-4- (4-ethoxyphenyl) -1- (3
Synthesis of -phenoxyphenyl) pentan-1-ol 4-methyl-4- (4-ethoxyphenyl) -1- (3
-Phenoxyphenyl) pent-2-yn-1-ol
1.0 g was dissolved in 50 ml of acetic acid, and 5% palladium-
After adding 200 mg of carbon, the catalytic hydrogenation reaction was carried out at room temperature while shaking under atmospheric pressure. Theoretical amount of hydrogen (12
(0 ml) was absorbed, the reaction solution was filtered, the solution was poured into water, and the mixture was extracted with ethyl acetate. The extract was washed successively with water, aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography to obtain 0.72 g of the target compound as a pale yellow oil.

Refractive index 1.5752 (24 ° C.) NMR (CDCl ₃ , δ value) 1.4 (t, 3H), 1.5 (s, 6H), 1.7 (m, 4H), 4.0 (q, 2H), 4.5 (m, 1H), 6.6 to 7.4 (m, 13H) Synthesis Example 2 4-Methyl-4- (4-ethoxyphenyl) -1- (3
Synthesis of -phenoxyphenyl) pentylethyl ether (Compound (1)) 4-Methyl-4- (4-ethoxyphenyl) -1- (3
-Phenoxyphenyl) pentan-1-ol 1.0 g,
110 mg (60%) of sodium hydride and 10 ml of dimethylformamide were placed in a reaction vessel and stirred at 20 ° C for 30 minutes, 0.3 ml of ethyl bromide was added, and the mixture was stirred at 50 ° C for 3 hours. The reaction solution was poured into 5% hydrochloric acid water (10 ml) and extracted with ethyl acetate. The extract was washed successively with water and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography to obtain 0.92 g of the desired product.

Refractive index 1.5522 (23.5 ° C.) NMR (CDCl ₃ , δ value) 1.23 (s, 6H), 1.28 (t, 3H), 1.5 (m, 4H), 3.3 ( dd, 1H), 4.0 (q, 2H), 6.7 to 7.4 (18H) When the compound of the present invention is used as an active ingredient of insecticides and acaricides, no other ingredients are added, Although it may be used as it is, usually, it is mixed with a solid carrier, a liquid carrier, a gaseous carrier, a surfactant, other formulation auxiliary agents, baits or the like, or impregnated into a base material such as an incense stick or a mat, Emulsions, wettable powders, powders, granules, oils, aerosols, fumigants such as mosquito coils and electric mosquito mats, fuming agents such as fogging, non-heat fumigants, poison baits and the like are used.

The content of the compound of the present invention as an active ingredient in these preparations is 0.01% to 95% by weight. As a solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut flour, urea,
Fine powders or granules of ammonium sulfate, synthetic hydrous silicon oxide and the like can be mentioned, and liquid carriers include kerosene, kerosene and other aliphatic hydrocarbons, benzene, toluene, xylene, methylnaphthalene and other aromatic hydrocarbons, dichloroethane, trichloroethylene. , Halogenated hydrocarbons such as carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, cellosolve,
Acetone, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, diethyl ether, dioxane,
Examples thereof include ethers such as tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethylsulfoxide, vegetable oils such as soybean oil and cottonseed oil. Examples of the gaseous carrier include CFC gas, LPG (liquefied petroleum gas), dimethyl ether and the like. Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate ester salts, naphthalene sulfone. Examples thereof include anionic surfactants such as acid formalin condensates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of formulation adjuvants such as sticking agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein,
Examples of the stabilizer include gelatin, CMC (carboxymethyl cellulose), pine oil, agar and the like, and examples of the stabilizer include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oils, epoxidized oils, and the like. Examples thereof include surfactants, antioxidants such as BHT and BHA, fatty acid salts such as sodium oleate and calcium stearate, and fatty acid esters such as methyl oleate and methyl stearate.

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 0.2 parts each of the compounds (1) to (17) of the present invention, 2 parts xylene and 97.8 parts white kerosene are mixed to obtain an oil solution.

Formulation Example 2 10 parts of each of the compounds (1) to (17) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are mixed well to obtain an emulsion.

Formulation Example 3 20 parts of the present compound (1), 10 parts of fenitrothion,
3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 65 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the present compound (2), 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a dust.

Formulation Example 5 5 parts of the compound (3) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 62 parts of kaolin clay are well pulverized and mixed, and after adding water and kneading well, Granulate and dry to obtain granules.

Formulation Example 6 The present compound (4) 0.05 part, tetramethrin 0.2 part,
Resmethrin 0.05 parts, xylene 7 parts, deodorant kerosene 32.7
Parts are mixed and dissolved, filled in an aerosol container, a valve portion is attached, and then 60 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve portion to obtain an aerosol.

Formulation Example 7 0.3 g of the d-trans primary chrysanthemic acid ester of allethrin was added to 0.3 g of the compound (5) of the present invention, dissolved in 20 ml of methanol, and a carrier for mosquito coil (tab powder: lees powder: wood powder) was added. 3; 5: 1
99.4 g of the mixture) is uniformly stirred and mixed, after evaporating methanol, 150 ml of water is added, and the mixture thoroughly kneaded is molded and dried to obtain a mosquito coil.

These formulations are used as they are or after diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
It can also be used as a mixture with herbicides, plant growth regulators, fertilizers, soil conditioners and the like.

When the compound of the present invention is used as an insecticidal or acaricidal agent, its application amount is usually 5 g to 500 g per 10 ares, and when the emulsion, wettable powder or the like is diluted with water and applied, the application concentration is 10 ppm. It is up to 1000 ppm, and powders, granules, oils, aerosols, etc. are applied to the formulation without any dilution.

Next, a test example is shown. The compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison and control are shown by the compound symbols in Table 2.

Test Example 1 13 g of a 200-fold diluted solution (equivalent to 500 ppm) of 2 ml of an emulsion of the compound of the present invention obtained according to Formulation Example 2 in 13 g
Soaked in the artificial bait for Japanese common lotus, 11 cm in diameter
In a polyethylene cup. Ten of the 4th instar larvae of Spodoptera litura were released therein, and after 6 days, life and death were investigated and the mortality rate was calculated (2 repetitions).

The results are shown in Table 3.

Test Example 2 A polyethylene cup having a diameter of 5.5 cm was covered with a paper of the same size, and 0.7 ml of a predetermined concentration diluted with water of the emulsion of the compound of the present invention and the reference compound prepared according to Formulation Example 2 was placed on the paper. Dropwise, 30 mg of sucrose was uniformly added as a bait.
Release 10 female adult houseflies in it, cover with 48
After a lapse of time, the life and death thereof were examined and the LC ₅₀ value (50% lethal concentration) was determined (repeated twice).

The results are shown in Table 4.

Test Example 3 Rice stalks (about 12 cm in length) were immersed for 1 minute in a dilute solution of an emulsion of the compound of the present invention and a control compound described below obtained in accordance with Formulation Example 2 at a predetermined concentration with water. After air-drying, rice stalks were placed in a test tube, and 10 adult strains of leafhopper leafhoppers were released, and one day later, life and death were investigated, and LC ₅₀ value (50% lethal concentration) was determined (2 repetitions).

The results are shown in Table 5.

Experimental Example 4 Ten adult females of the spider mite, M. angustifolia, per leaf were infested with the pot value tsurunashiengen (primary leaf stage) 7 days after sowing.
It was stored in a thermostatic chamber at 5 ° C. After 6 days, 15 ml per pot of a chemical solution prepared by diluting the emulsion of the compound of the present invention and the control compound described below prepared in accordance with Formulation Example 2 with water to 500 ppm of the active ingredient was sprayed on the turntable, and at the same time, 2 ml of the same solution was irrigated with soil. did. After 8 days, the degree of damage of each plant due to spider mites was investigated.

The criteria for effectiveness are: -No damage is observed.

+: Some damage is recognized.

: Same damage as untreated area.

And The results are shown in Table 6.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C07C 43/29 C 8619-4H C07D 317/54 (72) Inventor Toshihiko Yano Takashizuka Takashi, Hyogo Prefecture 4 2-2-1 Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Masachika Hirano 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A general formula [Wherein R ₁ is a lower alkyl group, a lower alkoxyl group,
Represents a lower alkenyloxy group, a lower haloalkyl group, a halogen atom or a fluorine-substituted lower alkoxyl group,
R ₂ represents a hydrogen atom or a halogen atom, and R ₁ and R ₂ together represent a methylenedioxy group. R ₃
And R ₄ each represent a methyl group, or R ₃ and R ₄ represent an ethylene group or a 1,1-difluoroethylene group. R ₅ represents a lower alkyl group, a lower haloalkyl group, a lower alkenyl group or a lower alkynyl group, and R ₆ represents a hydrogen atom or a fluorine atom. ] The benzyl ether derivative shown by these. 2. General formula [In the formula, R ₅ represents a methyl group or an ethyl group, and R ₆ represents a hydrogen atom or a fluorine atom. ] The benzyl ether derivative of Claim 1 shown by these. 3. General formula [In the formula, R ₅ represents a methyl group or an ethyl group, and R ₆ represents a hydrogen atom or a fluorine atom. ] The benzyl ether derivative of Claim 1 shown by these. 4. A general formula [Wherein R ₁ is a lower alkyl group, a lower alkoxyl group,
Represents a lower alkenyloxy group, a lower haloalkyl group, a halogen atom or a fluorine-substituted lower alkoxyl group,
R ₂ represents a hydrogen atom or a halogen atom, and R ₁ and R ₂ together represent a methylenedioxy group. R ₃
And R ₄ each represent a methyl group, or R ₃ and R ₄ represent an ethylene group or a 1,1-difluoroethylene group. R ₅ represents a lower alkyl group, a lower haloalkyl group, a lower alkenyl group or a lower alkynyl group, and R ₆ represents a hydrogen atom or a fluorine atom. ] An insecticide and acaricide containing the benzyl ether derivative represented by the following as an active ingredient.